1-(hydroquinonylalkylphenyl)-3 carbalkoxy-4(arylazo)-5-pyrazolones



United States Patent M 3,306,891 1-(HYDRGQUlN8NYLALKYLPHENYD-3 CARB- ALKOXY-4 (ARYLAZO)-5-PYRAZOLONES Milton Green, Newton Center, Mass., assignor to Polaroid Corporation, Cambridge, Mass., a corporation of Delaware No Drawing. Filed Aug. 9, 1963, Ser. No. 301,198 7 Claims. (Cl. 250-162) This invention relates to photography and more particularly to novel chemical compounds for use in products, compositions and processes for the development of photosensitive silver halide elements.

This application is a continuation-in-part of my copending application Serial No. 130,498, filed August 10, 1961, now abandoned. The photographic utilization of the novel compounds of this invention is claimed in my copending application Serial No. 301,181, filed concurrently herewith, now US. Patent No. 3,141,772, issued July 21, 1964.

A principal object of this invention is to provide novel chemical compounds.

Another object is to provide novel syntheses for preparing the novel compounds of this invention.

Another object of the present invention is to provide novel processes and compositions for the development of silver halide emulsions, in which colored developing agents are used to develop a latent image.

Another object is to provide novel processes and compositions for the development of silver halide emulsions, in which the novel developing agent is capable of developing a latent image and imparting a reversed or positive colored image of said latent image to a superposed imagereceiving material.

A further object is to provide novel products, processes and compositions suitable for use in preparing monochromatic and multichromatic photo-graphic images.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the products and compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.

For a fuller understand of the nature and objects of the invention, reference should be had to the following detailed description.

The novel photographic developing agents employed in this invention possess the properties of both a dye and a developing agent; thus they may be referred to as dye developers. The nature of these dye developers will be described hereinafter.

The photographic processes and compositions disclosed herein are particularly useful in the treatment of an exposed silver halide emulsion, whereby a positive dye image may be imparted to another element, herein referred to as image-carrying or image-receiving element.

US. Patent No. 2,983,606, issued May 9, 1961, to Howard G. Rogers, discloses diffusion transfer processes wherein a photographic negative material, such as a photographic element comprising an exposed silver halide emulsion is developed in the presence of a dye developer to impart to an image-receiving layer a reversed or positive dye image of the developed image by permeating into said emulsion layer a suitable liquid processing composition and bringing said emulsion layer into superposed relationship with an appropriate image-receiving layer.

It is an object of this invention to provide additional dye developers suitable for use in such processes.

fihbfigl Patented Feb. 28, 1967 In carrying out the process of this invention, a photosensitive element containing a silver halide emulsion is exposed and wetted with a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in the dark, and the photosensitive element superposed, prior to, during or after wetting, on an imagereceiving element. In a preferred embodiment, the photosensitive element contains a layer of dye developer, and the liquid processing composition is applied to the photosensitive element in a uniform layer as the photosensitive element is brought into superposed position with an imagereceiving element. The liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby providing an imagewise distribution of unoxidize-d dye developer dissolved in the liquid processing composition. This immobilization is apparently, at least in part, due to a change in the solubility characteristics of the dye developer upon oxidation, and especially as regards its solubility in alkaline solutions. It also may be due, in part, to a tanning effect on the emulsion by the oxidized developing agent. tion of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer. Under certain circumstances, the layer of the liquid processing composition may be utilized as the image-receiving layer. The image-receiving layer receives a depthwise diffusion, from the emulsion, of unoxidized dye developer, without appreciably disturbing the imagewise distribution thereof, to provide a reversed or positive, colored image of the developed image. The image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer. If the color of the diffused dye developer is affected by changes in the pH of the image-receiving element, this pH may be adjusted in accordance with well-known techniques to provide a pH affording the desired color. Imbibition periods of approximately one minute have been found to give good results, but this contact period may be adjusted where necessary to compensate for variations in temperature or other conditions. The desired positive image is revealed by stripping the image-receiving element from the photosensitive element at the end of the imbibition period.

The dye developers of this invention may be utilized in the photosensitive element, for example, in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element or in the liquid processing composition. In a preferred embodiment, a coating or layer of the dye developer is placed behind the silver halide emulsion, i.e., on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the image-receiving element when in superposed relationship therewith. Placing the dye developer behind the emulsion layer, as in the preferred embodiment, has the advantage of providing increased contrast in the positive image, and also minimizes any light-filtering action by the colored dye developer. In this preferred embodiment, the layer of dye developer may be applied by using a coating solution containing about 0.5 to 8%, by weight, of the dye developer. Similar concentrations may be used if the dye developer is utilized as a component of the liquid processing composition. In an especially useful mode of dispersing the dye developers in the photosensitive elements, the dye developer is dissolved in a water-immiscible solvent and then dispersed in a gelatin coating solution.

The liquid processing composition above referred to At least part of this imagewise distribucomprises at least an aqueous solution of an alkaline compound, for example, diethylamine, sodium hydroxide or sodium carbonate, and may contain the dye developer. In some instances, it may contain a minor amount of a conventional developing agent. If the liquid processing composition is to be applied to the emulsion by being spread thereon, preferably in a relatively thin, uniform layer, it may also include a viscosity-increasing compound constituting the film-forming material of the type which, when said composition is spread and dried, will form a relatively firm and relatively stable film. A preferred film-forming material is a high molecular weight polymer such as a polymeric, water-soluble ether inert to an alkali solution, as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose. Other film-forming materials or thickening agents whose ability to increase viscosity is substantially unaffected when left in solution for a long period of time may also be used.

The novel compounds of the present invention may be represented by the formula:

QN=N- |1CO-Z Ar-(M)..Y

wherein Q is a phenyl or naphthyl group, X is a hydrogen, halogen, lower alkyl, lower alkoxy, sulfonamido or trifluoromethyl radical, said X being located ortho to said N==N- group, R is a lower alkoxy, halogen, lower alkyl, trifluoromethyl or sulfonarnido radical, and p is an integer from to 4 inclusive.

In a preferred embodiment Q is a substituted phenyl radical, n is l, and Y is a para-dihydroxyphenyl radical. Such compounds may be represented by the formula:

wherein R 2, X, Z and M have the same meaning as above.

As examples of alkylene radicals comprehended by the radical M, mention may be made of radicals such as -CH CH -CH2-- H-CHrand CH CH CH In the preferred embodiment, M is a lower alkylene group, e.g., less than 6 carbons, and more preferably an ethylene or propylene group. It should be understood that M may be an alkylene group comprising 6 or more carbon atoms provided that the resulting chemical compound is capable of being dissolved in the photographic liquid processing composition, and its oxidation product rendered immobile.

As noted above, Q may be derived from any amine which is capable of diazotization. When Q is a phenyl radical, in addition to the ortho substituent X, the phenyl radical may also contain other substituents, above desig-- nated R in the 3, 4, 5 or 6 position or any combination thereof. The particular substituent selected and its specific position may be determined by one skilled in the art guided by the teachings of the present invention and with due regard to the substituents etfect on the color, solubility and light stability of the compound.

As examples of substituents represented as R mention may be made of methyl, ethyl, chloro, methoxy, and ethylsulfonarnido. It should also be understood that K may be further substituted, if desired.

The dye developers of this invention, compared with yellow pyrazolone azo dye developers described in the copending application of Elkan R. Blout, Milton Green and Howard G. Rogers, Serial No. 144,816, filed October 18, 1961, now US. Patent No. 3,134,672, issued May 26, 1964, as a continuation-in-part of Serial No. 612,- 045, filed September 25, 1956 (now abandoned), have improved silver halide developing properties and increased ligh stability characteristics. Thus, for example, it has been found that compounds IV and XI, infra, develop approximately 3 to 4 times as much silver (as measured by optical silver density) than l-phenyl-3-N-n-hexylcarboxamido 4 [pw-hydroquinonylethyl)-phenylazo]- S-pyrazolone in one minute under the same conditions, and in the absence of any other silver halide developing agent. In addition, any tendency toward fading of the instant novel yellow dye developers is not accompanied by a browning of the yellow dye developer. It has also been found that the above enumerated superior photographic properties, particularly the light stability, of these dye developers may be further enhanced when the ortho su'bstituent X is other than hydrogen, that is, a halogen, trifiuoromethyl, alkyl, or alkoxy radical.

As examples of novel chemical compounds within the H scope of the present invention, mention may be made of the following:

1-(4'-hydroquinonylethylphenyl) -3-carbethoxy-4- (2' ,6 dimethylphenylazo)-5-pyrazolone (XXVI) l a [4 (B [4"' methyl 2,5 dihydroxyphenyllethyl) phenyll 3 carbethoxy 4. (2,4,6, trlniethylphenylazo)-5-pyraz01one wherein Q X, R and p have the same meaning as above, and coupling the diazotized compound into a compound of the formula:

wherein Z, Ar, n and M have the same meaning as above, and Y is the protected derivative of the orthoor paradihydroxyphenyl group, preferably the acylated derivative thereof; and removing the protective groups of Y The protecting groups are removed prior to photographic utilization of the dyes, for example, removal of the acyloxy protective groups to provide thereby hydroxyl groups, the removal being accomplished, for example, by hydrolysis in the presence of alkali.

It will be understood that suitable precautions should be taken during the hydrolysis step to avoid hydrolysis also of the i -ooz group in the 3-position. The acyloxy protective groups of Y are less stable to hydrolysis than the ester group in the 3-position and may be removed, therefore, with relatively mild hydrolysis reaction conditions which will leave the ester group in the 3-position unaffected.

The term acyloxy is intended to signify the grouping 0 ll DG-O wherein D is an aryl, alkyl, aryloxy, or alkoxy group. The terms alkyl and aryl as employed herein are intended to include substituted aryl and alkyl groups, for example, aralkyl and alkaryl groups.

The compounds of Formula D which may be prepared by diazotizing and reacting a compound of the formula:

with a substituted ester of succinic acid, are disclosed and claimed in the copending application of Milton Green and Phylis T. Moore, Serial No. 130,489, filed April 10, 1961, now abandoned and replaced by copending application Serial No. 412,221, filed November 18, 1964, now U.S. Patent No. 3,252,990, issued May 24, 1966.

Suitable substituted esters of succinic acid may be prepared according to the method set out in Org. Synthesis Coll. vol. 11, p. 262.

Compounds within Formula E, when 11:1, that may be used in this invention, are disclosed and claimed in the copending US. application of Milton Green and Helen P. Husek, Serial No. 805,673, filed April 13, 1959, now US. Patent No. 3,019,254, issued January 30, 1962, and in the copending application of Elkan R. Blout, Milton Green and Howard G. Rogers, Serial No. 144,- 816, filed October 18, 1961, now U.S. Patent No. 3,134,- 672, issued May 26, 1964, as a continuation-in-part of Serial No. 612,045, filed September 25, 1956 (now abandoned). Examples of additional compounds which may be O-acylated to form compounds within Formula E are disclosed and claimed in the copending US. application of Elkan R. Blout, Milton Green, Myron S. Simon, Howard G. Rogers and Robert B. Woodward, Serial No. 98,287, filed March 27, 1961, and now US. Patent No. 3,236,893. Compounds within Formula E, when 11:0, that may be used in this invention are disclosed in the copending US. application of Myron S. Simon, Serial No. 196,523, filed May 21, 1962, now US. Patent No. 3,183,089, issued May 11, 1965, and which is a continuation-in-part of application Serial No. 612,053, filed September 25, 1956, now abandoned. It has also been found convenient to use the amine salt of compounds within Formula (E), which are also disclosed in the above-cited copending application, in the preparation of compounds of this invention.

The following nonlimiting examples illustrate the preparation of dye developers within the scope of this invention:

Example I A solution of 2 grams of 2,4-dimethylaniline, 2.7 ml. of concentrated hydrochloric acid and ml. of water was prepared and cooled to 0.5 C. A solution of 0.76 gram of sodium nitrate in 5 ml. of water was added with stirring. Stirring was continued 10 minutes and then a solution of 3 grams of 1-(p-[2',5-diacetoxyphenethyl] phenyl)-3-carbethoxy-S-pyrazolone, 10 grams of sodium bicarbonate, 200 ml. of acetone and 100 ml. of water was added dropwise, with the temperature maintained at C., until a spot test with resorcinol showed a slight excess. After stirring for an hour, the mixture was acidified, with hydrochloric acid, filtered, washed with water and dried with suction. The solid dye was then added to 500 ml. of methyl Cellosolve in a 1 liter 3- necked flask. Nitrogen was allowed to bubble through the mixture for minutes at room temperature. An oxygen-free solution of 0.65 gram of sodium hydroxide in ml. of water was added to the mixture and nitrogen again allowed to bubble through the mixture for 90 minutes. 10 ml. of concentrated hydrochloric acid was then added to the mixture. The product was then precipitated by the addition of Water and separated. The resulting product, 1 (4" hydroquinonylethylphenyl)-3- carbethoxy-4-(2,4-dimethylphenylazo) 5 pyrazolone, melted at 96101 C.

Example II 2,6-dimethylaniline was diazotized and coupled into 1- (p-[2,5-diacetoxyphenethyl]phenyl) 3 carbethoxy-5- pyrazolone according to the procedure of Example I. The resulting product, 1-(4"-hydroquinonylethylphenyl)- 3-carbethoxy-4-(2',6 dimethylphenylazo)-5-pyrazolone, melted at 170175 C.

Example III p-Toluidine was diazotized and coupled into 1-(p-[2, 5'-diacetoxyphenethyl] phenyl)-3-carbethoxy-5-pyrazolone according to the procedure of Example I. The resulting product, 1-(4"-hydroquinonylethylphenyl)-3-carbethoxy-4- (4-methylphenylazo -5-pyrazolone, melted at 207-211 C. with decomposition.

Example 1V 4-N-diethylsulfonamidoaniline was diazotized and coupled into 1-(p-[2,5-diacetoxyphenethyl] phenyl)-3-carbethoxy-5-pyrazolone according to the procedure of Example I. The resulting product, 1-(4"-hydroquinonylethylphenyl) 3 carbethoxy 4-(4-diethylsulfonamidophenylazo)-5-pyrazolone, melted at 242245 C. with decomposition.

Example V 2,3-dimethylaniline was diazotized and coupled into l-(p-[2',5-diacetoxyphenethyl]-phenyl) 3 carbethoxy- S-pyrazolone according to the procedure of Example I. The resulting product, 1-(4"-hydroquinonylethylphenyl) 3-carbethoxy-4-(2,5 dimethylphenylazo)-5-pyrazolone, melted at 115-122 C. with decomposition.

Example VI 2,4-dimethylaniline was diazotized and coupled into 1 (p [2,5 diacetoxyphenylpropyl] phenyl) 3- carbethoxy-S-pyrazolone according to the procedure of Example V. The resulting product, 1-(4"-hydroquinonylpropylphenyl) 3 carbethoxy 4 (2',3' dimethylphenylazo)-5-pyrazolone, melted at 100l05 C.

Example VII 2,4,6-trimethylaniline was diazotized and coupled into 1 (p [2,5' diacetoxyphenethyl] phenyl) 3 carbethoxy-S-pyrazolone according to the procedure of Example I. The resulting product, l-(4-hydroquinonylethylphenyl) 3 carbethoxy 4 (2,4,6' trimethylphenylazo)-5-pyrazolone, melted at 185-188 C.

Example VIII l-naphthylamine was diazotized and coupled into 1- (p [2,5 diacetoxyphenethyl] phenyl) 3 carbethoxy-5-pyrazolone according to the procedure of Example I. The resulting product, l-(4-hydroquinonylethyl- 12 phenyl) 3 carbethoxy 4 (1' naphthylazo) 5- pyrazolone, melted at 134140 C.

Example IX 2-methoxyaniline was diazotized and coupled into 1- (p [2,5 diacetoxyphenethyl] phenyl) 3 carbethoxy-5-pyrazolone according to the procedure of Example I. The resulting product, 1-(4-hydroquinonylethylphenyl)-3-carbethoxy 4 (2' methoxyphenylazo 5- pyrazolone, melted at 228232 C.

Example X 2-chloro-4-methylaniline was diazotized and coupled into 1 (p [2,5' diacetoxyphenethyl] phenyl) 3- carbethoxy-S-pyrazolone according to the procedure of Example I. The resulting product, 1-(4"-hydroquinonylethylphenyl) 3 carbethoxy 4 (2' chloro 4-methylphenylazo)-5-pyrazolone, melted at 106113 C.

Example XI 2,6-diethylaniline was diazotized and coupled into 1- (p [2,5' diacetoxyphenethyl] phenyl) 3-carbethoxy- 5-pyraz0lone according to the procedure of Example I. The resulting product, 1-(4"-hydroquinonylethylphenyl)- 3 carbethoxy 4 (2,6 diethylphenylazo) 5 pyrazolone, melted at 155-157 C.

Example XII 2,5-di-methylaniline was diazotized and coupled into 1- (p [2,5 diacetoxyphenethyl] phenyl) 3 carbethoxy- 5-pyrazolone according to the procedure of Example I. The resulting product, 1(4"-hydroquinonylethylphenyl)- 3 carbethoxy 4 (2,5' dimethylphenylazo) 5 pyrazolone, melted at 130140 C.

Example XIII 2-methyl-4-chloroaniline was diazotized and coupled into 1 (p [2,5 diacetoxyphenethyl] phenyl) 3- carbethoxy-S-pyrazolone according to the procedure of Example I. The resulting product, 1-(4-hydroquinonylethylphenyl) 3 carbethoxy 4 (2' methyl 4- chlorophenylazo)-5-pyrazolone, melted at 143149 C.

Example XIV 2,4-dimethylaniline was diazotized and coupled into 1- p [2,5' diacetoxyphenyl] phenyl) 3 carbethoxy- S-pyrazolone according to the procedure of Example I. The resulting product, 1-(4-hydroquinonylphenyl)-3- carbethoxy 4 (2,4 dimethylphenylazo) 8 pyrazolone, melted at 128130- C.

Example XV 2,4-dimethylaniline acetate was diazotized and coupled into 1 (p [2,5' diacetoxyphenylpropyl] phenyl) 3- carbethoxy-S-pyrazolone according to the procedure of Example I. The resulting solid was hydrolyzed with sodium hydroxide in a nitrogen atmosphere. The product, 1 (4" hydroquinonylpropylphenyl) 3 carbethoxy- 4-(2',4'-dimethylphenylazo)-5-pyrazolone, melted at C.

Example XVI o-Aminobenzotrifiuoride was diazotized and coupled into 1 (p [2,5' diacetoxyphenethyl] phenyl) 3- carbethoxy-S-pyrazolone according to the procedure of Example I. The resulting product, l-(4-hydroquinonylethylphenyl) 3 carbethoxy 4 (2' trifluoromethylphenylazo)-5-pyrazolone melted at 118 C.

The novel chemical compounds of the present invention may also be used as intermediates in preparing the novel compounds of the copending application of Milton Green, Serial No. 301,197, filed August 9, 1963.

The dye developers of this invention are also useful in integral multilayer photosensitive elements for use in multicolor diffusion transfer processes. As an example of such photosensitive elements, mention may be made of the photosensitive elements disclosed and claimed in the copending U.S. application of Edwin H. Land and Howard G. Rogers, Serial No. 565,135, filed February 13, 1956, wherein at least two selectively sensitized photosensitive strata are superposed on a single support and are processed, simultaneously and without separation, with a single common image-receiving element. A suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer. In one of the preferred embodiments of photosensitive elements of this type, the dye developers are disposed in separate alkali-permeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.

The photosensitive elements within the scope of this invention may be used in roll film units which contain a plurality of photosensitive frames. The photosensitive elements of this invention are especially useful in composite roll film intended for use in a Polaroid Land Camera, or a similar camera structure such, for example, as the camera forming the subject matter of U.S. Patent No. 2,435,717, issued to Edwin H. Land on February 10, 1948. In general, such composite roll films comprise a photosensitive roll, a roll of image-receiving material and a plurality of pods containing an aqueous alkaline processing solution. The rolls and pods are so associated with each other that, upon processing, the photosensitive element may be superposed on the image-receiving element and the pods may be ruptured to spread the aqueous alkaline processing solution between the superposed elements. The nature and construction of the pods used in such units are well known to the art. See, for example, U.S. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin H. Land.

It will be noted that the liquid processing composition may contain one or more auxiliary or accelerating silver halide developing agents, such as p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol); benzylaminophenol; hydroquinone; a substituted hydroquinone such as tolu-hydroquinone, phenylhydroquinone, or 4'-methylphenylhydroquinone; or a S-pyrazolidone such as l-phenyl-3-pyrazolidone. These silver halide developing agents are substantially colorless, at least in their unoxidized form. It is possible that some of the dye developer oxidized in exposed areas may be oxidized by an energy transfer reaction with oxidized auxiliary developing agent.

In addition, development may be effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed and claimed in the copending application of Milton Green and Howard G. Rogers, Serial No. 50,851, filed August 22, 1960, now U.S. Patent No. 3,173,786, issued March 16, 1965.

The dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional photosensitive films, plates or papers to obtain black and white, monochromatic or toned prints or negatives. By way of example, a developer composition suitable for such use may comprise an aqueous solution of approximately 12% of the dye developer, 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide. After development is completed, any unreacted dye developer is washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble. The expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye, whereas monochromatic is intended to designate dye images free of silver.

It should be noted that the dye developers of this medium are self-suflicient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which the color is produced by a coupling reaction between a color former or coupler and the oxidized developing agent, as well as so-called auto-coupling processes in which color is obtained by a reaction of the oxidized developing agent with unoxidized developing agent.

It will be apparent that, by appropriate selection of the image-receiving element from among suitable known opaque and transparent materials, it is possible to obtain either a colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts here in set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of image-receiving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of such photographic materials are disclosed in U.S. Patent No. 2,647,049 to Edwin H. Land.

As examples of useful image-receiving materials, mention may be made of nylon, e.g., N-methoxy-methyl-polyhexamethylene adipamide, polyvinyl alcohol, and gelatin, particularly polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine. The image-receiving element also may contain a development restrainer, e.g., 1-phenyl-5-mercaptotetrazole, as disclosed in the copending application of Howard G. Rogers and Harriet W. Lute-s, Serial No. 50,849, filed August 212, 1960.

The dye developers herein set forth are also useful in the formation of colored images in accordance with the photographic products and processes described and claimed in US. Patent No. 2,968,554, issued to Edwin H. Land on January 17, 1961.

The novel compounds herein disclosed are also suitable for use as dyes for textile fibres, such as nylon.

In the preceding portions of the specification the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black.

Since certain changes may be made in the above products, compositions and proceses without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. A compound of the formula:

wherein R is selected from the group consisting of lower alkyl, lower alkoxy, chlorine, sulfonamido, and trifluoromethyl radicals; p is an integer from 0 to 4, inclusive; X is a radical selected from the group consisting of hydrogen, chlorine, lower alkyl, lower alkoxy, sulfonamido, and trifluoromethyl radicals, said X being located ortho to said -N=N group; Q is a radical selected from the group consisting of phenyl and naphthyl radicals; Ar is a phenylene radical; M is a lower alkylene radical; N is an integer from 0 to 1, inclusive; Y is a radical selected from the group consisting of orthoand para-dihydroxyphenyl radicals and lower alkyl and chlorine derivatives thereof; and Z is a lower alkyl radical. 

1. A COMPOUND OF THE FORMULA: 